The present invention relates to new compositions that provide useful catalysts for polymerizations.
Ancillary (or spectator) ligand-metal coordination complexes (e.g., organometallic complexes) and compositions are useful as catalysts, additives, stoichiometric reagents, monomers, solid state precursors, therapeutic reagents and drugs. Ancillary ligand-metal coordination complexes of this type can be prepared by combining an ancillary ligand with a suitable metal compound or metal precursor in a suitable solvent at a suitable temperature. The ancillary ligand contains functional groups that bind to the metal center(s), remain associated with the metal center(s), and therefore provide an opportunity to modify the steric, electronic and chemical properties of the active metal center(s) of the complex.
Certain known ancillary ligand-metal complexes and compositions are catalysts for reactions such as oxidation, reduction, hydrogenation, hydrosilylation, hydrocyanation, hydroformylation, polymerization, carbonylation, isomerization, metathesis, carbon-hydrogen activation, carbon-halogen activation, cross-coupling, Friedel-Crafts acylation and alkylation, hydration, dimerization, trimerization, oligomerization, Diels-Alder reactions and other transformations.
One example of the use of these types of ancillary ligand-metal complexes and compositions is in the field of polymerization catalysis. In connection with single site catalysis, the ancillary ligand offers opportunities to modify the electronic and/or steric environment surrounding an active metal center. This allows the ancillary ligand to create possibly different polymers. Certain polymerization catalysts are known. See U.S. Pat. No. 4,336,360, EP Application No. 0 343 734 and Japanese Kokai Patent 09-255713, each of which is incorporated herein by reference. Likewise EP 343,734 discloses catalysts compositions for use in producing polyketone polymers, preferably polymers of carbon monoxide. The catalysts compositions are based upon a palladium compound, an anion of an acid having a pKa less than 2 and a compound represented by the formula R1R2M1xe2x80x94Rxe2x80x94M2xe2x80x94R3, where R1 and R2 are aryl groups, M1 is P or As, M2 is S or Se, R3 is a hydrocarbyl group and R is a bridging group having at least two carbons.
It is always a desire to discover new catalysts that will catalyze or assist in catalysis of reactions differently from known systems. This invention provides new catalyst compositions that may catalyze polymerization reactions differently, including more efficiently and selectively than known systems.
The invention disclosed herein is a new catalyst comprising metal-ligand complexes or compositions of metal precursors and ligands that catalyze polymerization and copolymerization reactions, particularly with monomers that are olefins, diolefins or otherwise acetylenically unsaturated. These compositions may also polymerize monomers that have polar functionalities in homopolymerizations or copolymerizations. The new catalyst compositions are prepared by combining a suitable ligand with a suitable metal precursor and, optionally, a suitable activator. The ligands of the composition are characterized by the general formula: 
wherein each R1, R2, and R3 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof; optionally, R1 and R2 are joined together in a ring structure and/or R1 or R2 is joined together with X in a ring structure; also optionally, R3 and X are joined in a ring structure; E is selected from the group consisting of nitrogen, phosphorus, arsenic and antimony (provided however that when E=N, X is not a benzylic group bound to N through the CH2 of the benzylic group); and X is a covalent bridging moiety. Suitable metal precursors are characterized by the formula: M(L)n where L represents any neutral or charged ligand capable of stabilizing the metal precursor, M represents any transition metal and n is a number from 0-6, provided however that when E=P and R3=H, then X cannot be R1R2Cxe2x80x94CR3R4 or R1C=CR2, where R1xe2x80x94R4 are as defined above. Suitable activators are known to those skilled in the art.
For catalysis, the ligands can be included in a composition including a suitable metal, where the said composition has catalytic properties. Also, the ligands can be coordinated with a metal precursor to form metal-ligand complexes, which may be catalysts. Depending on the groups chosen for X, E, R1, R2, and R3 in the ligand (e.g., prior to reaction with the metal precursor), the metal-ligand complexes can be characterized by one of many different general formulas depending on how the ligand attaches to or coordinates with the metal.
Thus, in another aspect of the invention, a polymerization process is disclosed for monomers. The polymerization process involves contacting one or more monomers to the catalyst compositions or to the coordination complexes of this invention under polymerization conditions. The catalyst compositions or the coordination complexes may be active catalysts themselves or make be activated with a known activating technique or compound. The polymerization process can be continuous, batch or semi-batch and can be homogeneous or heterogeneous.
Further aspects of this invention will be evident to those of skill in the art upon review of this specification.
The inventions disclosed herein are metal complexes and compositions, which are useful as catalysts for chemical reactions, especially polymerization reactions.
As used herein, the phrase xe2x80x9ccharacterized by the formulaxe2x80x9d is not intended to be limiting and is used in the same way that xe2x80x9ccomprisingxe2x80x9d is commonly used. The term xe2x80x9cindependently selectedxe2x80x9d is used herein to indicate that the R groups, e.g., R1, R2, R3, R4, and R5 can be identical or different (e.g. R1, R2, R3, R4, and R5 may all be substituted alkyls or R1 and R2 may be a substituted alkyl and R3 may be an aryl, etc.). A named R group will generally have the structure that is recognized in the art as corresponding to R groups having that name. The terms xe2x80x9ccompoundxe2x80x9d and xe2x80x9ccomplexxe2x80x9d are generally used interchangeably in this specification, but those of skill in the art may recognize certain compounds as complexes and vice versa. For the purposes of illustration, representative certain groups are defined herein. These definitions are intended to supplement and illustrate, not preclude, the definitions known to those of skill in the art.
The term xe2x80x9calkylxe2x80x9d is used herein to refer to a branched or unbranched, saturated or unsaturated acyclic hydrocarbon radical. Suitable alkyl radicals include, for example, methyl, ethyl, n-propyl, i-propyl, 2-propenyl (or allyl), vinyl, n-butyl, t-butyl, i-butyl (or 2-methylpropyl), etc. In particular embodiments, alkyls have between 1 and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20 carbon atoms.
xe2x80x9cSubstituted alkylxe2x80x9d refers to an alkyl as just described in which one or more hydrogen atom to any carbon of the alkyl is replaced by another group such as a halogen, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, and combinations thereof Suitable substituted alkyls include, for example, benzyl, trifluoromethyl and the like.
The term xe2x80x9cheteroalkylxe2x80x9d refers to an alkyl as described above in which one or more hydrogen atoms to any carbon of the alkyl is replaced by a heteroatom selected from the group consisting of N, O, P, B, S, Si, Sb, Al, Sn, As, Se and Ge. The bond between the carbon atom and the heteroatom may be saturated or unsaturated. Thus, an alkyl substituted with a heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio, or seleno is within the scope of the term heteroalkyl. Suitable heteroalkyls include cyano, benzoyl, 2-pyridyl, 2-furyl and the like.
The term xe2x80x9ccycloalkylxe2x80x9d is used herein to refer to a saturated or unsaturated cyclic non-aromatic hydrocarbon radical having a single ring or multiple condensed rings. Suitable cycloalkyl radicals include, for example, cyclopentyl, cyclohexyl, cyclooctenyl, bicyclooctyl, etc. In particular embodiments, cycloalkyls have between 3 and 200 carbon atoms, between 3 and 50 carbon atoms or between 3 and 20 carbon atoms.
xe2x80x9cSubstituted cycloalkylxe2x80x9d refers to cycloalkyl as just described including in which one or more hydrogen atom to any carbon of the cycloalkyl is replaced by another group such as a halogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio, seleno and combinations thereof. Suitable substituted cycloalkyl radicals include, for example, 4-dimethylaminocyclohexyl, 4,5-dibromocyclohept-4-enyl, and the like.
The term xe2x80x9cheterocycloalkylxe2x80x9d is used herein to refer to a cycloalkyl radical as described, but in which one or more or all carbon atoms of the saturated or unsaturated cyclic radical are replaced by a heteroatom such as nitrogen, phosphorous, oxygen, sulfur, silicon, germanium, selenium, or boron. Suitable heterocycloalkyls include, for example, piperazinyl, morpholinyl, tetrahydropyranyl, tetrahydrofuranyl, piperidinyl, pyrrolidinyl, oxazolinyl and the like.
xe2x80x9cSubstituted heterocycloalkylxe2x80x9d refers to heterocycloalkyl as just described including in which one or more hydrogen atom to any atom of the heterocycloalkyl is replaced by another group such as a halogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio, seleno and combinations thereof. Suitable substituted heterocycloalkyl radicals include, for example, N-methylpiperazinyl, 3-dimethylaminomorpholinyl and the like.
The term xe2x80x9carylxe2x80x9d is used herein to refer to an aromatic substituent which may be a single aromatic ring or multiple aromatic rings which are fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety. The common linking group may also be a carbonyl as in benzophenone or oxygen as in diphenylether or nitrogen in diphenylamine. The aromatic ring(s) may include phenyl, naphthyl, biphenyl, diphenylether, diphenylamine and benzophenone among others. In particular embodiments, aryls have between 1 and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20 carbon atoms.
xe2x80x9cSubstituted arylxe2x80x9d refers to aryl as just described in which one or more hydrogen atom to any carbon is replaced by one or more functional groups such as alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, alkylhalos (e.g., CF3), hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, and both saturated and unsaturated cyclic hydrocarbons which are fused to the aromatic ring(s), linked covalently or linked to a common group such as a methylene or ethylene moiety. The common linking group may also be a carbonyl as in benzophenone or oxygen as in diphenylether or nitrogen in diphenylamine.
The term xe2x80x9cheteroarylxe2x80x9d as used herein refers to aromatic rings in which one or more carbon atoms of the aromatic ring(s) are replaced by a heteroatom(s) such as nitrogen, oxygen, boron, selenium, phosphorus, silicon or sulfur. Heteroaryl refers to structures that may be a single aromatic ring, multiple aromatic ring(s), or one or more aromatic rings coupled to one or more non-aromatic ring(s). In structures having multiple rings, the rings can be fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety. The common linking group may also be a carbonyl as in phenyl pyridyl ketone. As used herein, rings such as thiophene, pyridine, isoxazole, phthalimide, pyrazole, indole, furan, etc. or benzo-fused analogues of these rings are defined by the term xe2x80x9cheteroaryl.xe2x80x9d
xe2x80x9cSubstituted heteroarylxe2x80x9d refers to heteroaryl as just described including in which one or more hydrogen atoms to any atom of the heteroaryl moiety is replaced by another group such as a halogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio, seleno and combinations thereof. Suitable substituted heteroaryl radicals include, for example, 4-N,N-dimethylaminopyridine.
The term xe2x80x9calkoxyxe2x80x9d is used herein to refer to the xe2x80x94OZ1 radical, where Z1 is selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocylcoalkyl, substituted heterocycloalkyl, silyl groups and combinations thereof as described herein. Suitable alkoxy radicals include, for example, methoxy, ethoxy, benzyloxy, t-butoxy, etc. A related term is xe2x80x9caryloxyxe2x80x9d where Z1 is selected from the group consisting of aryl, substituted aryl, heteroaryl, substituted heteroaryl, and combinations thereof. Examples of suitable aryloxy radicals include phenoxy, substituted phenoxy, 2-pyridinoxy, 8-quinalinoxy and the like.
As used herein the term xe2x80x9csilylxe2x80x9d refers to the xe2x80x94SiZ1Z2Z3 radical, where each of Z1 Z2, and Z3 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.
As used herein the term xe2x80x9cborylxe2x80x9d refers to the xe2x80x94BZ1Z2 group, where each of Z1 and Z2 is independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.
As used herein, the term xe2x80x9cphosphinoxe2x80x9d refers to the group xe2x80x94PZ1Z2, where each of Z1 and Z2 is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, cycloalkyl, heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl, silyl, alkoxy, aryloxy, amino and combinations thereof.
The term xe2x80x9caminoxe2x80x9d is used herein to refer to the group xe2x80x94NZ1Z2, where each of Z1 and Z2 is independently selected from the group consisting of hydrogen; alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl and combinations thereof.
The term xe2x80x9cthioxe2x80x9d is used herein to refer to the group xe2x80x94SZ1, where Z1 is selected from the group consisting of hydrogen; alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl and combinations thereof.
The term xe2x80x9cselenoxe2x80x9d is used herein to refer to the group xe2x80x94SeZ1, where Z1 is selected from the group consisting of hydrogen; alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl and combinations thereof.
The term xe2x80x9csaturatedxe2x80x9d refers to lack of double and triple bonds between atoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, and the like.
The term xe2x80x9cunsaturatedxe2x80x9d refers to the presence one or more double and triple bonds between atoms of a radical group such as vinyl, acetylenyl, oxazolinyl, cyclohexenyl, acetyl and the like.
Suitable ligands useful in this invention can be characterized by the general formula: 
wherein each R1, R2, and R3 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof; optionally, R1 and R2 are joined together in a ring structure and/or R1 or R2 is joined together with X in a ring structure; also optionally, R3 and X are joined in a ring structure; E is selected from the group consisting of nitrogen, phosphorus, arsenic and antimony (provided however that when E=N, X is not a benzylic group bound to N through the CH2 of the benzylic group); and X is a covalent bridging moiety, provided however that when E=P and R3=H, then X cannot be R1R2Cxe2x80x94CR3R4 or R1C=CR2, where R1xe2x80x94R4 are as defined above.
In more specific embodiments, R1 and R2 and R3 are independently selected from a group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl and silyl. Specific examples of R1 and R2 and R3 are hydrogen, methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl, cyclooctyl, phenyl, mesityl, 2,6-diisopropylphenyl, naphthyl, benzyl, trimethylsilyl, and the like. In those embodiments where R1 and R2 and joined together in a ring structure, the ring (including R1, R2 and E) has from 3 to 30 non-hydrogen atoms as part of the backbone of the ring. Specific examples of R1 and R2 together are ethylene (giving a 3-member ring), propylene (giving a 4-membered ring), butylene (giving a 5-membered ring), 3-oxopentylene (giving a 6-membered ring) and the like. In those embodiments where R1 or R2 is joined together with X in a ring structure, the ring (including R1 or R2 and X) has from 3 to 30 non-hydrogen atoms as part of the backbone of the ring. Specific examples of R1 or R2 with X together are ethylene (giving a 3-member ring), propylene (giving a 4-membered ring), butylene (giving a 5-membered ring), 3-oxopentylene (giving a 6-membered ring) and the like. In those embodiments where ether R3 is joined together with X in a ring structure, the ring (including R3 and X) has from 3 to 30 non-hydrogen atoms as part of the backbone of the ring. Specific examples of R3 and X together are ethylene (giving a 3-member ring), propylene (giving a 4-membered ring), butylene (giving a 5-membered ring), 3-oxopentylene (giving a 6-membered ring) and the like.
In a preferred embodiment, R1 and R2 and R3 are substituted or unsubstituted aryl groups, substituted or unsubstituted alkyl groups or substituted or unsubstituted cyclohexyl groups. If R1, R2, R3, are substituted phenyls, there may be 1, 2, 3, 4 or 5 substituents attached to carbon atoms in the phenyl ring. Each of these substituents may be independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof. More preferably, there are 1, 2 or 3 substituents on the substituted phenyl and the substituents are selected from the group consisting of chloro, fluoro, iodo, bromo, trifluoromethyl, methoxy, ethoxy, phenoxy, nitro, methyl, ethyl, propyl, isopropyl, butyl, tertiarybutyl, cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl, trimethylsilyl and isomers thereof.
More specifically X is a bridging group comprising an alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, aryl, or substituted aryl group. X may contain functional groups that may additionally bind to the metal.
Chiral ligands of the formulae described above are especially useful in this invention.
The ligands of this invention may be synthesized using known procedures. See, for example, Advanced Organic Chemistry, March, Wiley, N.Y. 1992 (4th Ed.). Once the desired ligand is formed, it may be combined with a metal atom, ion, compound or other metal precursor compound. In those embodiments where one of more of R1 or R2 or R3 is a hydrogen atom, the ligand may be deprotonated prior to combining the ligand with the metal precursor compound. In many applications, the ligands of this invention will be combined with such a metal compound or precursor and the product of such combination is not determined, if a product forms. For example, the ligand may be added to a reaction vessel at the same time as the metal or metal precursor compound along with the reactants. The metal precursor compounds may be characterized by the general formula M(L)n where M is a metal selected from the group consisting of Groups 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic Table of Elements and n is an integer that depends on the metal and the ligands L chosen for the metal, e.g., such as whether the ligands L are neutral or charged. In more specific embodiments, M is selected from the group consisting of Ti, Zr, Hf, V, Ta, Nb, Cr, W, Mo, Ru, Os, Co, Rh, Ir, Ni, Pd, Fe, Mn, Re, Cu, Zn and Pt. L is a ligand chosen from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, hydrido, thio, seleno, phosphino, amino, carboxylates, acetylacetates, and combinations thereof. n is 0, 1, 2, 3, 4, 5 or 6. When n is greater than 1, then each L is independently selected from the ligands above. Specific examples of suitable metal precursor compounds include Ti(CH2Ph)4, Zr(CH2Ph)4, Hf(CH2Ph)4, V(mesityl)3(THF), Ta(CH3)3(Cl)2, Nb(CH3)3(Cl)2, Ta(NMe2)3(Cl)2, Cr(CHTMS2)3, Cr(mesityl)2(THF), Cr(mesityl)2(THF)3, [Fe(mesityl)2]2, [Co(mesityl)2]2, Co(mesityl)3Li(THF)4, [Mn(mesityl)2]3, Cr(mesityl)3, Sc(CH(SiMe3)2)3, Y(CH(SiMe3)2)3, Ln(CH(SiMe3)2)3, Sc(O(2,6-(But)2C6H3))3, Y(O(2,6-(tBu)2C6H3))3, Ln(O(2,6-(But)2C6H3))3, Sc(O(2,6-(But)2-4-Me-C6H3))3, Y(O(2,6-(tBu)2-4-Me-C6H3))3, Ln(O(2,6-(But)2-4-Me-C6H3))3, Sc(N(SiMe3)2)3 Y(N(SiMe3)2)3, Ln(N(SiMe3)2)3, (where Ln =La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), Ni(acac)2, Pd(acac)2, Co(acac)3, Fe(acac)3, Fe(acac)2, Mn(acac)2, Cr(acac)2, Cr(acac)3, V(acac)3, V(O)(acac)3, Ni(TFA)2, Fe(TFA)2, Fe(TFA)3, Co(TFA)2, Mn(TFA)2, [Cr(TFA)2]2, Cr(TFA)3, V(TFA)3, CrCl3(THF)3, VCl3(THF)3, (COD)PdMeCl, [(cyclooctene)PdMeCl]2, (COD)PdMeOTf, [(allyl)PdCl]2, [(allyl)NiCl]2, [(CH3O2CC3H4)NiBr]2, [(allyl)NiTFA]2, (p-cymene)Ru(TFA)2(CH3CN), (p-cymene)Ru(mesityl)(TFA), (PPh3)4RuH2, (PPh3)2Ni(Ph)Cl, (PPh3)4Ni, (COD)2Ni, (py)2Ni(CH2SiMe3)2, Fe(C(SiMe3)3)2, Co(C(SiMe3)3)2, Mn(C(SiMe3)3)2, Ti(CH2CMe3)4, Zr(CH2CMe3)4, Hf(CH2CMe3)4, TiCl4, Ti(NMe2)4, Zr(NMe2)4, Hf(NMe2)4, Zr(NEt2)4, Ti(NMe2)2Cl2, Zr(N(SiMe3)2)2Cl2, Hf(N(SiMe3)2)2Cl2, Zr(TFA)4, Hf(TFA)4, Ti(TFA)2Cl2, TiCl3(THF)3, V(CH(SiMe3)2)3(THF), V(O-2,6-Prixe2x80x94C6H3)4Li(THF), Ta(NMe2)5, (TMEDA)NiMe2, (TMEDA)PdMe2, Ta(CH2CMe3)2Cl3, TaPh5, Co(PPh3)3CH3, [Co(PPh3)3H]2N2, and [Ni(PCy3)2]2N2 and the like. (TFA=trifluoroacetate; COD=1,5-cyclooctadiene; TMEDA=tetramethylethylenediamine; OTf=triflate; THF=tetrahydrofuran; Pri=isopropyl; py=pyridine; acac=acetylacetanoate; mesityl=2,4,6-Me3C6H2-, But=tertiary butyl.)In this context, the ligand to metal precursor compound ratio is in the range of about 0.01:1 to about 100:1, more preferably in the range of about 0.5:1 to about 20:1.
In other applications, the ligand will be mixed with a suitable metal precursor compound prior to or simultaneous with allowing the mixture to be contacted to the reactants. When the ligand is mixed with the metal precursor compound, a metal-ligand complex may be formed, which may be a catalyst. Depending on the substituents chosen for the ligand prior to reaction with the metal precursor compound, the metal complexes may be characterized by any of the following general formulae: 
wherein each R1, R2, R3, R4, R5, R6, R7, R8, and R9 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof; E is selected from the group consisting of nitrogen, phosphorus, arsenic and antimony (provided however that when E=N, X is not a benzylic group bound to N through the CH2 of the benzylic group); and X is a covalent bridging moiety, as defined above provided however that when E=P and R3=H, then X cannot be R1R2Cxe2x80x94CR3R4 or R1Cxe2x95x90CR2, where R1xe2x80x94R4 are as defined above. M is a transition metal selected from the group consisting of Groups 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic Table of Elements. Selection of the metal is most preferably dependent on the ligand structure. L is independently each occurrence, a neutral and/or charged ligand. Generally, L is a ligand chosen from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, hydrido, thio, seleno, phosphino, amino, carboxylates, acetylacetates, and combinations thereof; and n is 0, 1, 2, 3, 4, 5, or 6, when n is greater than 1, each L is independently selected from the ligands above.
Dimers, trimers or higher orders of the above are also useful to the invention. Additionally, examples where two or more metal atoms are bridged by one or more ligands are useful in the invention. Furthermore, two or more ligands may coordinate with a single metal atom. The nature of the metal complex or complexes formed most likely depends on the chemistry of the ligand and the metal precursor and the method of combining the ligand and metal precursor, such that a distribution of metal complexes may form with the number of ligands bound to the metal being greater than or less then the number of equivalents of ligands added relative to an equivalent of the metal precursor.
Within each of these formulae, specific examples include, but are not limited to: 
Dimers, trimers or higher orders of the above are also useful to the invention. Additionally, examples where two or more metal atoms are bridged by one or more ligands are useful in the invention. Furthermore, two or more ligands may coordinate with a single metal atom. The nature of the metal complex or complexes formed most likely depends on the chemistry of the ligand and the metal precursor and the method of combining the ligand and metal precursor, such that a distribution of metal complexes may form with the number of ligands bound to the metal being greater than or less then the number of equivalents of ligands added relative to an equivalent of the metal precursor.
The ligands may be supported, with or without the metal coordinated, on an organic or inorganic support. Suitable supports include silicas, aluminas, zeolites, polyethyleneglycols, polystyrenes, polyesters, polyamides, peptides and the like. Similarly, the metal may be supported with or without the ligand, on similar supports known to those of skill in the art.
Polymerization catalysis with the compositions and metal complexes of this invention is a particularly effective process. In particular, the complexes and compositions of this invention are active catalysts also for the polymerization of olefins, possibly in combination with an activator or activating technique. When an activator or activating technique is used, those of skill in the art may use alumoxanes, strong Lewis acids, compatible non-interfering activators and combinations of the foregoing. The foregoing activators have been taught for use with different compositions or metal complexes in the following references, which are hereby incorporated by reference in their entirety: U.S. Pat. Nos. 5,599,761, 5,616,664, 5,453,410, 5,153,157, 5,064,802, and EP-A-277,004. Preferred activators include methylalumoxane, trimethylaluminum, AgBF4, AgBPh4, NaBArxe2x80x24, H(OEt2)2BArxe2x80x24 and the like (where Arxe2x80x2 is a substituted aromatic, like perfluorophenyl or 3,5-(CF3)2(C6H3)). Ratios of neutral complex to activator are on the order of 1 to 1000 to 1000 to 1. A scavenger can also be used with this invention. Scavengers useful herein include the metal complexes, alumoxanes, aluminum alkyls and the like. Other additives that are standard for polymerization reactions can be used.
Suitable ion forming compounds useful as an activator in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and an inert, compatible, non-interfering, anion, Axe2x88x92. Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core. Mechanistically, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitrites. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions that comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially.
Preferably such activators may be represented by the following general formula:
(L*xe2x88x92H)d+(Adxe2x88x92
wherein, L* is a neutral Lewis base; (L*xe2x88x92H)+ is a Bronsted acid; Adxe2x88x92 is a non-interfering, compatible anion having a charge of d-, and d is an integer from 1 to 3. More preferably Adxe2x88x92 corresponds to the formula: [Mxe2x80x23+ Qh]dxe2x88x92 wherein h is an integer from 4 to 6; hxe2x88x923=d; Mxe2x80x2 is an element selected from Group 13 of the Periodic Table of the Elements; and Q is independently selected from the group consisting of hydride, dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, and substituted-hydrocarbyl radicals (including halosubstituted hydrocarbyl, such as perhalogenated hydrocarbyl radicals), said Q having up to 20 carbons. In a more preferred embodiment, d is one, i.e., the counter ion has a single negative charge and corresponds to the formula Axe2x88x92.
Activators comprising boron or aluminum which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula:
[L*xe2x88x92H]+[JQ4]xe2x88x92
wherein: L* is as previously defined; J is boron or aluminum; and Q is a fluorinated C1-20 hydrocarbyl group. Most preferably, Q is independently selected from the group selected from the group consisting of fluorinated aryl group, especially, a pentafluorophenyl group (i.e., a C6F5 group) or a 3,5-bis(CF3)2C6H3 group. Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are tri-substituted ammonium salts such as: trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethylanilinium tetra-(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl) borate, triethylammonium tetrakis(pentafluorophenyl) borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(secbutyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl) borate, trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate and N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl) borate; dialkyl ammonium salts such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, and dicyclohexylammonium tetrakis(pentafluorophenyl) borate; and tri-substituted phosphonium salts such as: triphenylphospnonium tetrakis(pentafluorophenyl) borate, tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate, and tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate; and N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. Preferred [L*xe2x88x92H]+ cations are N,N-dimethylanilinium and tributylammonium. Preferred anions are tetrakis(3,5-bis(trifluoromethyl)phenyl)borate and tetrakis(pentafluorophenyl)borate. In some embodiments, the most preferred activator is PbNMe2H+B(C6F5)4xe2x88x92.
Other suitable ion forming activators comprise a salt of a cationic oxidizing agent and a non-interfering, compatible anion represented by the formula:
(Oxe+)d(Adxe2x88x92)e
wherein: Oxe+ is a cationic oxidizing agent having a charge of e+; e is an integer from 1 to 3; and Adxe2x88x92, and d are as previously defined. Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag+, or Pb+2. Preferred embodiments of Adxe2x88x92 are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyl)borate.
Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion or silyl cation and a non-interfering, compatible anion represented by the formula:
C+Axe2x88x92
wherein: C+ is a C1-100 carbenium ion or silyl cation; and Axe2x88x92 is as previously defined. A preferred carbenium ion is the trityl cation, i.e. triphenylcarbenium. The silyl cation may be characterized by the formula Z1Z2Z3Si+ cation, where each of Z1 Z2, and Z3 is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl and combinations thereof. In some embodiments, a most preferred activator is Ph3C+B(C6F5)4xe2x88x92.
In addition, suitable activators include Lewis acids, such as those selected from the group consisting of tris(aryl)boranes, tris(substituted aryl)boranes, tris(aryl)alanes, tris(substituted aryl)alanes, including activators such as tris(pentafluorophenyl)borane. Other useful ion forming Lewis acids include those having two or more Lewis acidic sites, such as those described in WO 99/06413 or Piers, et al. xe2x80x9cNew Bifunctional Perfluoroaryl Boranes: Synthesis and Reactivity of the ortho-Phenylene-Bridged Diboranes 1,2-[B(C6F5)2]2C6X4 (X=H, F)xe2x80x9d, J. Am. Chem. Soc., 1999, 121, 3244-3245, both of which are incorporated herein by reference. Other useful Lewis acids will be evident to those of skill in the art. In general, the group of Lewis acid activators are within the group of ion forming activators (although exceptions to this general rule can be found) and the group tends to exclude the group 13 reagents listed below. Combinations of ion forming activators may be used.
Other general activators or compounds useful in a polymerization reaction may be used. These compounds may be activators in some contexts, but may also serve other functions in the polymerization system, such as alkylating a metal center or scavenging impurities. These compounds are within the general definition of xe2x80x9cactivator,xe2x80x9d but are not considered herein to be ion forming activators. These compounds include a group 13 reagent that may be characterized by the formula G13Rxe2x80x23xe2x88x92pDp where G13 is selected from the group consisting of Al, B, Ga, In and combinations thereof, p is 0, 1 or 2, each Rxe2x80x2 is independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl, heterocyclic and combinations thereof, and each D is independently selected from the group consisting of halide, hydride, alkoxy, aryloxy, amino, thio, phosphino and combinations thereof. In other embodiments, the group 13 activator is an oligomeric or polymeric alumoxane compound, such as methylalumoxane and the known modifications thereof. In other embodiments, a divalent metal reagent may be used that is defined by the general formula Mxe2x80x2Rxe2x80x22xe2x88x92pxe2x80x2Dpxe2x80x2 and pxe2x80x2 is 0 or 1 in this embodiment and Rxe2x80x2 and D are as defined above. Mxe2x80x2 is the metal and is selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Cd and combinations thereof In still other embodiments, an alkali metal reagent may be used that is defined by the general formula Mxe2x80x3Rxe2x80x2 and in this embodiment Rxe2x80x2 is as defined above. Mxe2x80x3 is the alkali metal and is selected from the group consisting of Li, Na, K, Rb, Cs and combinations thereof. Additionally, hydrogen and/or silanes may be used in the catalytic composition or added to the polymerization system. Silanes may be characterized by the formula SiRxe2x80x24xe2x88x92qDq where Rxe2x80x2 is defined as above, q is 1, 2, 3 or 4 and D is as defined above, with the proviso that there is at least one D that is a hydride.
The molar ratio of metal precursor:activator employed preferably ranges from 1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferably from 1:10 to 1:1. In a preferred embodiment of the invention mixtures of the above compounds are used, particularly a combination of a group 13 reagent and an ionic activator (i.e., those with a positive and negative charge). The molar ratio of group 13 reagent to ionic activator is preferably from 1:10,000 to 1000:1, more preferably from 1:5000 to 100:1, most preferably from 1:100 to 100:1. In a preferred embodiment, the ion forming activators are combined with a tri-alkyl aluminum, specifically trimethylaluminum, triethylaluminum, or triisobutylaluminum or with a di-alkyl aluminum hydride such as di-isobutyl aluminum hydride.
The compositions and catalysts herein may be used to polymerize ethylenically or acetylenically unsaturated monomers having from 2 to 20 carbon atoms either alone or in combination The compounds and catalysts of this invention also usefully polymerize functionalized monomers, such as acetates and acrylates. Monomers olefins, diolefms and acetylenically unsaturated monomers, including C2 to C20 xcex1-olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-norbornene, styrene, and mixtures thereof; additionally, 1,1-disubstituted olefins, such as isobutylene, either alone or with other monomers such as ethylene or C3 to C20 xcex1-olefins and/or diolefins. These definitions are intended to include cyclic olefins. Diolefins generally comprise 1,3-dienes such as (butadiene), substituted 1,3-dienes (such as isoprene) and other substituted 1,3-dienes, with the term substituted referring to the same types of substituents referred to above in the definition section. Diolefins also comprises 1,5-dienes and other non-conjugated dienes. The use of diolefins in this invention is typically in conjunction with another monomer that is not a diolefin. The styrene monomers may be unsubstituted or substituted at one or more positions on the aryl ring. One class of functionalized monomers can be characterized by the general formula H2Cxe2x95x90CHxe2x80x94FG, where FG is the functional group that contains at least one heteroatom (using the previous definition) or halogen (e.g., Cl, F, Br, etc.). Functionalized monomers include C1-C20 acrylates, C1-C20 methacrylates, acrylic acid, methacrylic acid, maleic anhydride, vinyl acetate, acrylonitrile, acrylamide, vinyl ethers, vinyl chloride, and mixtures thereof. The compositions of this invention may also be used to copolymerize two or more of the monomers described herein. Novel polymers, copolymers or interpolymers may be formed having unique physical and/or melt flow properties. Such novel polymers can be employed alone or with other polymers in a blend to form products that may be molded, cast, extruded or spun. End uses for the polymers made with the catalysts of this invention include films for packaging, trash bags, bottles, containers, foams, coatings, insulating devices and household items. Also, such functionalized polymers are useful as solid supports for organometallic or chemical synthesis processes.
Polymerization can be carried out in the Ziegler-Natta or Kaminsky-Sinn methodology, including temperatures of from xe2x88x92100xc2x0 C. to 400xc2x0 C. and pressures from atmospheric to 3000 atmospheres. Suspension, solution, slurry, gas phase or high-pressure polymerization processes may be employed with the catalysts and compounds of this invention. Such processes can be run in a batch, semi-batch or continuous mode. Examples of such processes are well known in the art. A support for the catalyst may be employed, which may be inorganic (such as alumina, magnesium chloride or silica) or organic (such as a polymer or cross-linked polymer). Methods for the preparation of supported catalysts are known in the art. Slurry, suspension, solution and high-pressure processes use a suitable solvent as known to those skilled in the art.
Suitable solvents for polymerization are noncoordinating, inert liquids. Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, perfluorinated hydrocarbons such as perfluorinated C4-10 alkanes, and aromatic and alkylsubstituted aromatic compounds such as benzene, toluene, and xylene. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, butadiene, cyclopentene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, isobutylene, styrene, divinylbenzene, allylbenzene, vinyltoluene (including all isomers alone or in admixture), vinyl chloride, acrylonitrile, acrylates, vinyl acetate, methacrylates, 4-vinylcyclohexene, and vinylcyclohexane. Mixtures of the foregoing are also suitable.
Other additives that are useful in a polymerization reaction may be employed, such as scavengers, promoters, etc.
The ligands, metal complexes and compositions of this invention can be prepared and tested for catalytic activity in one or more of the above reactions in a combinatorial fashion. Combinatorial chemistry generally involves the parallel or rapid serial synthesis and/or screening or characterization of compounds and compositions of matter. U.S. Pat. No. 5,776,359 and WO 98/03521, both of which are incorporated herein by reference, generally disclose combinatorial methods. In this regard, the metal precursors, ligands, complexes or compositions may be prepared and/or tested in rapid serial and/or parallel fashion, e.g., in an array format. When prepared in an array format, for example, the metal precursors, activators and/or ligands may take the form of an array comprising a plurality of compounds wherein each compound can be characterized by the general formula 
where R1, R2, R3, X, E are as defined above. Typically, each member of the array will have differences so that, for example, R1 in a first region of the array may be different than R1 in a second region of the array. Other variables may also differ from region to region in the array. The array may also be of metal-ligand complexes or composition as discussed above; for example the members of the array may be characterized by any of the formulae I, II, III, IV, V, VI, VII, VIII or IX, discussed above. In a preferred embodiment, when E=P and R3=H, then X cannot be R1R2Cxe2x80x94CR3R4 or R1Cxe2x95x90CR2, where R1-R4 are as defined above
In such a combinatorial array, typically each of the plurality of compounds has a different composition or stoichiometry and, typically each composition or complex is at a selected region on a substrate such that each is isolated from the other compositions or complexes. This isolation can take many forms, typically depending on the substrate used. If a flat substrate is used, there may simply be sufficient space between regions so that there cannot be interdiffusion between compositions or complexes. As another example, the substrate can be a microtiter or similar plate having wells so that each compsition or complex is in a region separated from other compounds in other regions by a physical barrier. The array may also comprise a parallel reactor or testing chamber.
The array typically comprises at least 8 compounds, complexes or compositions each having a different chemical make-up, meaning that there is, typically, at least one different atom or bond differentiating the members in the array or different ratios of the components referred to herein (with components referring to metal precursors, activators, group 13 reagents, solvents, monomers, supports, etc.). In other embodiments, there are at least 20 compounds, complexes or compositions on or in the substrate each having a different chemical formula or ratio of components. In still other embodiments, there are at least 40 or 90 or 124 compounds, complexes or compositions on or in the substrate each having a different chemical formula or ratio of components. Because of the manner of forming combinatorial arrays, it may be that each compound, complex or composition may not be worked-up, purified or isolated, and for example, may contain reaction by-products or impurities or unreacted starting materials.
The catalytic performance of the ligands of this invention alone or in combination with a suitable metal precursor or metal-ligand coordination complexes of this invention can be tested in a combinatorial or high throughput fashion. Polymerizations can also be performed in a combinatorial fashion, see, e.g., provisional U.S. patent application Ser. Nos. 60/096,603, filed Aug. 13, 1998, Ser. No. 09/211,982, filed Dec. 14, 1998 and Ser. No. 09/239,223, filed Jan. 29, 1999, each of which is incorporated by reference herein. High throughput screening can also be performed optically and in parallel, for example, as disclosed in U.S. patent applications Ser. No. 08/947,085, filed Oct. 8, 1997, and Ser. No. 08/946,135, filed Oct. 7, 1997, each of which is incorporated by reference.